CO加氢合成低碳混合醇催化体系研究新进展

CO加氢合成低碳混合醇是C1化学研究的重要内容之一,近年来低碳混合醇在燃料和化工领域的应用价值逐步凸现,相关研究也受到越来越普遍的关注.本文就CO加氢合成低碳混合醇的催化剂体系、反应机理、合成工艺及应用等方面的最新进展进行了综述.     

一氧化碳加氢合成低碳燃料醇催化剂的研究

以甲醇为主(～75%),异丁醇为辅(～15%)的低碳混合醇称为低碳燃料醇,它与汽油有良好的掺合能,可以掺入汽油作为代用燃料。本工作目的是在较缓和条件下研制合成低碳燃料醇催化剂,进行催化剂评价试验,考察其反应特性,并进行1000小时稳定性试验。1.实验方法催化剂评价试验在固定床反应装置上进行。反应管为φ15×480mm。催化剂20—30     

还原态Mo-Ni-K/C催化剂上CO加氢合成低碳混合醇

ＣＯ加氢合成低碳混合醇已成为Ｃ１化学的一个重要分支．目前用于这一过程的催化剂大都是改性的甲醇合成、ＦＴ合成或二者组合的催化剂．自从８０年代中期美国Ｄｏｗ化学品公司和联合碳化物公司首先发现ＭｏＳ２基催化剂具有优良的催化合成醇反应性能和良好的抗硫中毒能...     

CO+H_2合成低碳醇的毛细管色谱分析

CO+H_2合成低碳醇是由煤制取液体燃料和化工原料的主要途径之一。随催化剂不同,可以合成以甲醇和异丁醇为主,用作汽油掺合剂的低碳燃料醇,也可得到以正构醇为主,用以生产化工原料用的醇类的低碳化学醇。这两种合成醇中异构体多,水份多,因此用填充柱分离,常有一定困难。1987年徐淑英用OV-101毛细管柱对     

沉淀方法对FeMnCu/ZnO合成低碳醇催化剂性能的影响

以分步连续沉淀法和共沉淀法制备了一系列FeMnCu/ZnO复合氧化物合成低碳醇催化剂，对其CO加氢合成低碳混合醇的反应性能进行了考察，并用ICP、XRD、BET、H2-TPR对其结构进行了表征。结果表明，沉淀方法不同对催化剂的催化性能有较大的影响。在T503K、P=8.0MPa，GHSV=8000h－1，H2/CO＝2(体积比)的条件下, 分步沉淀法制备的FeMnCu/ZnO催化剂醇的收率和C2+OH的质量分数均高于共沉淀法制备的催化剂。其中“Fe atop Cu”催化剂醇的收率最高，达到0.26g/mLcat·h，同时“Fe atop Cu”催化剂C2+OH的质量分数也最高，可达31.72%。XRD研究表明，分步沉淀法制备的催化剂促进了CuO和ZnO的分散，提高了催化剂的催化性能。BET测试结果表明，分步沉淀法有扩孔的作用，有利于长链醇的生成。TPR研究发现，共沉淀法制备的催化剂Cu物种较难还原，这是共沉淀催化剂合成醇性能较低的原因之一。     

Co在超细Mo-Co-K催化剂合成低碳醇中的作用

采用BET、XPS和TPD表征手段对超细Mo-Co-K催化剂的织构、表面结构和吸附行为进行了研究，结合催化剂的合成低碳醇性能，论证了Co在超细Mo-Co-K催化剂合成低碳醇中的作用。Co的加入提高了催化剂合成低碳醇的活性和选择性，同时也提高了催化剂的比表面并促进了微孔的形成，催化剂的催化性能与其织构之间呈现出很好的顺变关系。Co对催化剂中可能作为合成低碳醇活性中心的低价Mo物种的电子结合能值影响较小。Co的加入降低了H2和CO在催化剂表面的强吸附中心的吸附强度，从而有利于合成低碳醇反应的发生。研究结果表明，Co仅仅是作为结构助剂，通过调变催化剂的织构和催化剂表面的H2及CO的强吸附中心而影响其合成低碳醇性能的。     

合成气制低碳燃料醇工业侧线模试

在接近工业操作条件下,综合考察催化剂制备放大、工业粒度催化剂、反应器放大及工业合成气等放大效应对合成气制低碳燃料醇催化反应的影响。在模试反应器中采用多段蛇管换热及移热与催化剂床层合理稀释,从而保证反应温度均匀。在模试中较系统地考察了温度、压力、空速及合成气中CO_2含量对合成低碳燃料醇反应的影响。在400—405℃,14—15MPa,尾气空速4000h~(-1)条件下进行了1000小时寿命试验,结果良好。低碳燃料醇的时空产率为0.21—0.25升醇/升催化剂/小时。在燃料醇中,甲醇占74—77%,异丁醇12—15%。本工作为合成气制低碳燃醇料工业试验装置的基础设计提供数据。     

煤间接液化研究进展

报道了中国科学院山西煤炭化学研究所“七五”期间在煤间接液化研究方面的进展，包括煤基合成气合成发动机燃料及合成气制低碳燃料醇技术的研究开发￣［１］。其中煤基合成气合成发动机燃料已完成８０～１００ｔ／ａ中间试验，燃料油收率达１００ｇ／ｍ￣３（ＣＯ＋Ｈ＿２），汽油辛烷值（马达法）达８０，尾气热值达１２５４ｋＪ／ｍ￣３。合成气制低碳燃料醇技术研究开发已完成升级模式，在燃料醇组成中，甲醇占７１～７７％，异丁醇１２～１５％，时空产率为０．２１～０．２５Ｌａｌｃ／Ｌｃａｔ·ｈ．参考文献６篇。     

La促进CuCo催化剂上合成气转化制低碳醇的研究

利用超声辅助的反相共沉淀法制备了合成气选择转化制低碳醇用CuCo基催化剂。研究稀土La助剂对CuCo基复合氧化物催化剂结构的影响和催化性能的促进作用,借助X射线衍射(XRD)、N₂吸附等温线(BET)和程序升温脱附(CO-TPD)等测试技术对催化剂进行表征,并以CO加氢合成低碳醇为模型反应对其催化性能进行评价。结果表明,La助剂的添加使催化剂晶粒细化,显著加大了比表面积,促进了合成醇活性位的形成,提高了催化剂表面较强吸附CO物种的浓度,从而明显提高催化剂的活性与C_2＋醇选择性,有效调节了低碳混合醇中甲醇的含量。     

不同助剂的硫化MoO3／ZrO2催化剂上CO加氢合成低碳混合醇的反应性能

研究了碱金属离子（Li^ 、Na^ 、K^ 、Cs^ ）和碱土金属离子（Ca^2 、Sr^2 、Ba^2 ）为助剂的硫化MoO3/ZrO2催化剂上CO加氢合成低碳混合醇的反应性。碱金属离子（Li^ ,K^ )、特别是钾离子为助剂的催化剂比之碱土金属离子助剂具有 更好的合成低碳醇的活性和选择性。从一系列的实验和分析发现，硫化K－MoO3/ZrO2的合 成低碳醇的活性和选择性强烈依赖于钾助剂的含量和反应条件。合理 选择 最佳K／Mo比（－0.5原子比）、反应压力、温度和空速可以获得较好的合成醇活性和选择性。     

Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles

High-temperature solution phase reaction of iron(III) acetylacetonate, Fe(acac)(3), with 1,2-hexadecanediol in the presence of oleic acid and oleylamine leads to monodisperse magnetite (Fe(3)O(4)) nanoparticles. Similarly, reaction of Fe(acac)(3) and Co(acac)(2) or Mn(acac)(2) with the same diol results in monodisperse CoFe(2)O(4) or MnFe(2)O(4) nanoparticles. Particle diameter can be tuned from 3 to 20 nm by varying reaction conditions or by seed-mediated growth. The as-synthesized iron oxide nanoparticles have a cubic spinel structure as characterized by HRTEM, SAED, and XRD. Further, Fe(3)O(4) can be oxidized to Fe(2)O(3), as evidenced by XRD, NEXAFS spectroscopy, and SQUID magnetometry. The hydrophobic nanoparticles can be transformed into hydrophilic ones by adding bipolar surfactants, and aqueous nanoparticle dispersion is readily made. These iron oxide nanoparticles and their dispersions in various media have great potential in magnetic nanodevice and biomagnetic applications.     

CO/H_2合成混合醇Cu-Co-Fe催化剂的组成和铁的分散行为(英文)

Cu-Co-Fe catalysts were prepared by coprecipitation of Cu-Co nitrate solutions with Na2CO3 and impregnation of iron nitrate on the Cu-Co precipitates by incipient wetness method; and their phase structure, composition and iron dispersion behavior were studied by XRD, SEM and SAM techniques. The catalyst precursor consists of CuO, Co3O4 and (-Fe2O3. The intensity of XRD peak of Fe2O3 changes as the relative content of iron varies. No X-ray diffraction peak of iron oxide appears unless the content of iron surpasses a threshold value.     

有机添加物对Cu-Co-Fe合成醇催化剂的修饰作用

 采用并流共沉淀法制备了Cu-Co-Fe合成醇催化剂,通过改变有机添加物,对Cu-Co-Fe催化剂前驱物的结构和表面状态进行修饰和改性,考察了不同有机添加物对催化剂结构的影响规律. 不同添加物可以修饰调节催化剂的晶粒大小、比表面积和孔径分布. 加入草酸或丙烯酰胺,可使CuO(111)和Co3O4(110)晶粒度增大,比表面积减小,孔径较大的过渡孔分数增大. 柠檬酸为添加物时,催化剂中CuO和Co3O4晶粒度较小,比表面积较大,孔径主要分布在小于10 nm的细孔区.     

Co-Fe/SBA-15与过一硫酸盐联用非均相催化降解水中染料罗丹明B

由于硫酸根自由基(SO4?-)的强氧化性,基于SO4?-的高级氧化技术受到人们的高度关注.采用过渡金属活化过一硫酸盐(PMS)产生SO4?-用以分解有机物,反应体系简单,反应条件温和,且不需要额外的能量供给,因此,成为人们优先选用的方法,其中,采用高效、环境友好的非均相过渡金属催化剂活化PMS处理难降解有机物成为研究热点.本文研究了非均相CoFe/SBA-15-PMS体系对水中难降解染料罗丹明B(RhB)的降解.以SBA-15为载体, Co(NO3)2·6H2O和Fe(NO3)3·9H2O为前驱物,采用一步等体积浸渍法制备了CoFe/SBA-15,通过X射线衍射(XRD)、N2吸附-脱附、扫描电镜(SEM)、能谱(EDS)、透射电镜(TEM)和振动样品磁强计(VSM)等对其进行了表征.考察了焙烧温度、Co与Fe的负载量对CoFe/SBA-15催化性能的影响和该催化剂的重复使用性能,还考察了RhB降解动力学及催化剂CoFe/SBA-15投加量、氧化剂PMS投加量和反应物(RhB和PMS)初始浓度对其性能的影响,探讨了RhB的降解机理.结果表明：对于催化剂CoFe/SBA-15,合成焙烧后在SBA-15上负载的Fe、Co化合物主要是CoFe2O4复合物,它作为催化剂的活性中心负载在SBA-15的孔道内外.制备的焙烧温度对CoFe/SBA-15催化性能几乎无影响,但对Co浸出影响显著.与SBA-15相比,催化剂10Co9.5Fe/SBA-15-700(Co和Fe负载量分别为10 wt%和9.5 wt%,焙烧温度700 oC)的比表面积、孔体积和孔径均减小,分别为506.1 m2/g,0.669 cm3/g和7.4 nm,但仍然保持SBA-15的有序六方介孔结构.该催化剂以棒状体的聚集态存在,聚集体直径大于0.25μm,其磁化强度为8.3 emu/g,因此,可通过外磁铁容易地从水中分离.相比之下,10Co9.5Fe/SBA-15-700具有最佳的催化性能和稳定性,可使RhB的降解率达到96%以上, Co的浸出量小于32.4μg/L.在CoFe/SBA-15和PMS共存下, RhB的降解符合一级动力学方程, RhB降解速率随CoFe/SBA-15和PMS投加量的增加和初始反应物浓度的减小而提高.淬灭实验结果表明,在CoFe/SBA-15, PMS和RhB水溶液体系中,存在的主要活性自由基为SO4?-,它是由CoFe/SBA-15活化PMS产生的,对RhB的降解起决定性的作用. RhB降解过程的UV-vis结果表明, RhB的降解途径主要是蒽环打开, SO4?-优先攻击RhB的有色芳香烃环,然后RhB进一步分解为小分子有机物. CoFe/SBA-15循环使用10次仍能保持高催化活性和稳定性,在每次反应中RhB的降解率均大于84%, Co和Fe的浸出量均分别小于72.1和35μg/L. CoFe/SBA-15作为高效、环境友好的非均相催化剂可有效地活化PMS产生SO4?-降解水中RhB,具有实际应用的潜力.     

Fischer-Tropsch synthesis by nano-structured iron catalyst

Effects of nanoscale iron oxide particles on textural structure, reduction, carburization and catalytic behavior of precipitated iron catalyst in Fischer-Tropsch synthesis (FTS) are investigated. Nanostructured iron catalysts were prepared by microemulsion method in two series. Firstly, Fe2O3, CuO and La2O3 nanoparticles were prepared separately and were mixed to attain Fe/Cu/La nanostructured catalyst (sep-nano catalyst); Secondly nanostructured catalyst was prepared by co-precipitation in a water-in-oil microemulsion method (mix-nano catalyst). Also, conventional iron catalyst was prepared with common co-precipitation method. Structural characterizations of the catalysts were performed by TEM, XRD, H2 and CO-TPR tests. Particle size of iron oxides for sep-nano and mix-nano catalysts, which were determined by XRD pattern (Scherrer equation) and TEM images was about 20 and 21.6 nm, respectively. Catalyst evaluation was conducted in a fixed-bed stainless steel reactor and compared with conventional iron catalyst. The results revealed that FTS reaction increased while WGS reaction and olefin/paraffin ratio decreased in nanostructured iron catalysts.     

静电纺丝法制备定向排列的铁氧体纳米纤维

以聚乙烯吡咯烷酮(PVP)和金属硝酸盐为原料,采用改进的静电纺丝法制备了直径均匀、表面光滑、定向排列的Co0.8Zn0.2Fe2O4/PVP纳米纤维前驱体,经热处理后得到定向排列的铁氧体纳米纤维.对前驱体纤维的热分解过程及Co0.8Zn0.2Fe2O4(CZFO)的结构、物相及形貌进行了表征.结果表明,在空气中经550～950℃热处理3 h后均得到纯相、结晶良好的尖晶石型钴锌铁氧体;在2000 r/min转速下收集的复合纤维形貌最佳,直径约300 nm;经750℃热处理后纤维直径约为70 nm,室温下测得饱和磁化强度为66.1 A.m2/kg,矫顽力达到最大值6.6 A/m,表明钴锌尖晶石型铁氧体单畴临界尺寸约为44 nm.与CoFe2O4相比,CZFO的饱和磁化强度升高,矫顽力下降,并且CZFO的纤维与粉末的磁特性有明显的区别.     

Correlation between spin-orbital coupling and the superparamagnetic properties in magnetite and cobalt ferrite spinel nanocrystals

The superparamagnetic properties of CoFe2O4 and Fe3O4 nanocrystals have been systematically investigated. The observed blocking temperature of CoFe2O4 nanocrystals is at least 100 deg higher than that of the same sized Fe3O4 nanocrystals. The coercivity of CoFe2O4 nanocrystals at 5 K is over 50 times higher than the same sized Fe3O4 nanocrystals. The drastic difference in superparamagnetic properties between the similar sized spherical CoFe2O4 and Fe3O4 (or FeFe2O4) spinel ferrite nanocrystals was correlated to the coupling strength between electron spin and orbital angular momentum (L-S) in magnetic cations. Compared to the Fe2+ ion, the effect of much stronger spin-orbital coupling at Co2+ lattice sites leads to a higher magnetic anisotropy and results in the dramatic discrepancy of superparamagnetic properties between CoFe2O4 and Fe3O4 nanocrystals. These results provide some insight to the fundamental understanding of the quantum origin of superparamagnetic properties. Furthermore, they suggest that it is possible to control the superparamagnetic properties through magnetic coupling at the atomic level in spinel ferrite nanocrystals for various applications.     

Fe3O4 and gamma-Fe2O3 nanoparticles for the adsorption of Co2+ from aqueous solution

The adsorption of Co2+ ions from nitrate solutions using iron oxide nanoparticles of magnetite (Fe3O4) and maghemite (gamma-Fe2O3) has been studied. The adsorption of Co2+ ions on the surface of the particles was investigated under different conditions of oxide content, contact time, solution pH, and initial Co2+ ion concentration. It has been found that the equilibrium can be attained in less than 5 min. The maximum loading capacity of Fe3O4 and gamma-Fe2O3 nanoparticles is 5.8 x 10(-5) and 3.7 x 10(-5) mol m(-2), respectively, which are much higher than the previously studied, iron oxides and conventional ion exchange resins. Co2+ ions were also recovered by dilute nitric acid from the loaded gamma-Fe2O3 and Fe3O4 with an efficiency of 86 and 30%, respectively. That has been explained by the different mechanisms by including both the surface and structural loadings of Co2+ ions. The surface adsorption of Co2+ on Fe3O4 and gamma-Fe2O3 nanoparticles has been found to have the same mechanism of ion exchange reaction between Co2+ in the solution and proton bonded on the particle surface. The conditional equilibrium constants of surface adsorption of Co2+ on Fe3O4 and gamma-Fe2O3 nanoparticles have been determined to be log K=-3.3+/-0.3 and -3.1+/-0.2, respectively. The structural loading of Co2+ ions into Fe3O4 lattice has been found to be the ion exchange reaction between Co2+ and Fe2+ while that into gamma-Fe2O3 lattice to fill its vacancy. The effect of temperature on the adsorption of Co2+ was also investigated, and the value of enthalpy change was determined to be 19 kJ mol(-1).     

钴负载的凹凸棒土催化剂的制备、表征及其催化氧化性能

利用浸渍法制备了一系列不同钴含量的凹凸棒土催化剂,使用X射线衍射(XRD),X射线光电子能谱(XPS)和红外光谱(IR),详细研究了催化剂的构效关系,结果表明钴和载体发生作用形成了CoAl2O4和CoFe2O4两种晶相.研究了催化剂在无溶剂条件下对环己烯的催化氧化性能,实验结果表明Co-AT-1(钴含量0.46%)催化剂对环己烯氧化表现出较好的催化活性.催化剂的有效活性成分是CoFe2O4.     

多级结构还原氧化石墨烯包覆的钴铁氧体的合成及电化学性能

以水滑石为前驱体合成微米花/纳米片多级结构过渡金属复合氧化物CoFe2O4,一种高性能锂离子电池负极材料。 通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术手段对其进行结构表征,发现得到的复合氧化物为单一晶相,且具有多级结构。 电化学性能测试表明,得到的负极材料具有高比容量和倍率性能。 通过还原氧化石墨烯(rGO)对CoFe2O4进行表面包覆制备CoFe2O4/rGO,其循环稳定性得到大幅度提高。